The objective of this research is to extend recent tests of the hypothesis that phosphates may be labilized to substitution; (1) if they can be made to mediate electron transfer processes; (2) if they can be coordinated to Lewis acids freshly produced by oxidation; or (3) if they can be coordinated to reducing agents capable of adding electron density to P(V) atoms. ATP, PPPi, and PPi hydrolyses have been coupled to the oxidation of VO2 ions by H2O2. Polyphosphates inhibit this process. The redox induced hydrolyses can differentiate between ATP greater than PPPi greater than PPi and pA pA greater than ApA. Ap is not hydrolyzed. Systematic study of the kinetics, mechanisms, and stoichiometries of these hydrolyses will be undertaken. The redox activation of phosphodiester bonds in DNA and RNA will be explored as a mechanism of mutagenesis. These studies will be extended to redox systems involving MoO3 ions and MoO2 2ions. Vanadium(IV) and Mo(V) d1 species will be used as spin probes of polyphosphate complexes. VO3 complexes with nucleoside triphophates hydrolyze 10 to the 6th power times faster than simple ATP. These unstable molecular complexes will be tested as phosphorylation systems for ADP. Oxidation of lactic acid by Cr(VI) will be performed in the presence of Pi to attempt to form phosphoenolpyruvate in a simple system by "oxidative phosphorylation". Complexes of reducing agents such as Sn2 ions, Fe2 ions, and other metals will be studied to determine their effects upon the hydrolysis of ATP. The effect of oxidizing these ions in the presence of ATP will also be examined. The ultimate objective of these studies is to understand various chemical means of activating P-O-P bonds.